Phthalic diester derivatives and electron donors

ABSTRACT

A phthalic acid diester derivative represented by a specific formula and an electron donor used in an olefin polymerization catalyst containing the phthalic acid diester derivative as an effective component. The electron donor can produce polymers with a high stereoregularity at an extremely high polymerization activity and high yield, and exhibit a high response to hydrogen.

FIELD OF THE INVENTION

The present invention relates to an electron donor of an olefinpolymerization catalyst, a novel phthalic acid diester derivative usedas a plasticizer for resins such as vinyl chloride, a component forintermediates for the preparation of various compounds, and an electrondonor used in the olefin polymerization catalyst containing the phthalicacid diester derivative.

BACKGROUND ART

Conventionally, phthalic acid diesters have been used as a commonplasticizer for vinyl chloride. Diethyl phthalate, dibutyl phthalate,and di-iso-octyl phthalate are typical phthalic acid diesters. In thetechnology for polymerizing olefins, typically propylene, in thepresence of a solid catalyst comprising magnesium and titanium as majorcomponents, an electron donor (an internal electron donor) is added tothe solid catalyst to improve the stereoregularity of the formed polymerand the polymerization activity. A number of reports have proposed theuse of specific phthalic acid esters as such an electron donor.

As a prior art using a phthalic acid diester as one of the components ofthe olefin polymerization catalyst, Japanese Unexamined PatentPublication No. (hereinafter referred to as JP-A) 63310/1982 and JP-ANo. 63311/1982, for example, disclose a method of polymerizing olefinshaving three or more carbon atoms using a combined catalyst comprising asolid catalyst component containing a magnesium compound, titaniumcompound, and an electron donor such as a diester compound, e.g.,phthalic acid ester, an organoaluminum compound, and an organosiliconcompound having a Si—O—C linkage. JP-A 6006/1989 discloses a solidcatalyst component for olefin polymerization containing analkoxymagnesium, titanium tetrachloride, and dibutyl phthalate. Thesolid catalyst component was proven to be successful to some extent inproducing a stereoregular propylene polymer at a high yield.

The polymers produced using these catalysts are used in a variety ofapplications including formed products such as parts of vehicles andhousehold electric appliances, containers, and films. These products aremanufactured by melting polymer powders produced by the polymerizationand by forming the melted polymer using any one of various molds. Inmanufacturing formed products, particularly large products, by injectionmolding, melted polymers are sometimes required to have high fluidity(melt flow rate). Accordingly, a number of studies have been undertakento increase the melt flow rate of polymers.

The melt flow rate greatly depends on the molecular weight of thepolymers. In the polymer industry, hydrogen is generally used as amolecular weight regulator for polymers in the polymerization ofolefins. In this instance, a large quantity of hydrogen is usually addedto produce low molecular weight polymers which are the polymers having ahigh melt flow rate. However, the quantity of hydrogen which can beadded is limited because of the pressure resistance of the reactor fromthe viewpoint of safety. In order to add a larger amount of hydrogen,the partial pressure of monomers to be polymerized has to be decreased.The decrease in the partial pressure, however, is accompanied by adecrease in the productivity. Additionally, use of a large amount ofhydrogen may bring about a problem of cost. Development of a catalystcapable of producing polymers with a high melt flow rate by using asmaller amount of hydrogen, in other words, a catalyst which has a highactivity to hydrogen or high response to hydrogen and which produces ahighly stereoregular polymer at a high yield has therefore been desired.In the above-mentioned prior art, however, it is not sufficient to solvesuch a problem.

Accordingly, an object of the present invention is to provide a novelphthalic acid diester derivative useful as one of the components for anolefin polymerization catalyst, particularly a catalyst for thepolymerization of propylene or ethylene, having a high response tohydrogen, which can produce polymers having high stereoregularity in anextremely high activity and high yield, and an electron donor used as anolefin polymerization catalyst containing the phthalic acid diesterderivative as an effective component.

DISCLOSURE OF THE INVENTION

The present inventors have conducted extensive studies to solve theproblems in conventional technologies relating to the catalysts for thepolymerization of olefins. As a result, the present inventors havediscovered a novel phthalic acid diester derivative which is extremelyeffective as an electron donor used as one of the components of such acatalyst. Confirmation of such an effect has led to the completion ofthe present invention.

Specifically, the above object is achieved in the present invention by aphthalic acid diester derivative of the following formula (1),

wherein R¹ is an alkyl group having 1 to 8 carbon atoms or a halogenatom; R² and R³ may be either identical or different, representing analkyl group having 1 to 12 carbon atoms; and n, which indicates thenumber of R¹, is 1 or 2, provided that when n is 2, the two R¹ groupsmay be either identical or different.

The above object is further achieved in the present invention by anelectron donor used in a catalyst for the polymerization of olefinscomprising a phthalic acid diester derivative of the above formula (1)as an effective component.

BEST MODE FOR CARRYING OUT THE INVENTION

In the phthalic acid diester derivative of the present invention, givenas examples of the alkyl group having 1 to 8 carbon atoms represented byR¹ of the formula (1) are a methyl group, an ethyl group, a n-propylgroup, an iso-propyl group, a n-butyl group, an iso-butyl group, at-butyl group, a n-pentyl group, an iso-pentyl group, a neopentyl group,a n-hexyl group, an iso-hexyl group, a 2,2-dimethylbutyl group, a2,2-dimethyl pentyl group, a iso-octyl group, and a 2,2-dimethylhexylgroup. As halogen atoms represented by R¹, a fluorine atom, a chlorineatom, a bromine atom, and an iodine atom can be given. Of these groupsrepresented by R¹, preferable groups are a methyl group, an ethyl group,a t-butyl group, a chlorine atom, a fluorine atom, and a bromine atom,with the methyl group, t-butyl group, chlorine atom, fluorine atom, andbromine atom being particularly preferable.

The groups represented by R² or R³ include a methyl group, an ethylgroup, a n-propyl group, an iso-propyl group, a n-butyl group, aniso-butyl group, a t-butyl group, a n-pentyl group, an iso-pentyl group,a neopentyl group, a n-hexyl group, an iso-hexyl group, a2,2-dimethylbutyl group, a 2,2-dimethyl pentyl group, an iso-octylgroup, a 2,2-dimethylhexyl group, a n-nonyl group, an iso-nonyl group, an-decyl group, an iso-decyl group, and a n-dodecyl group. Of these, anethyl group, a n-butyl group, an iso-butyl group, a t-butyl group, aneopentyl group, an iso-hexyl group, and an iso-octyl group arepreferable, with an ethyl group, a n-butyl group, a neopentyl group, andan iso-hexyl group being particularly preferable.

The symbol n, which indicates the number of R¹, is 1 or 2, provided thatwhen n is 2, the two R¹ groups may be either identical or different.When n=1, the substituent R¹ replaces the hydrogen atom at the 3, 4, or5 position of the phthalic acid diester derivative, and when n=2, R¹replaces the hydrogen atoms at the 4 and 5 positions.

Preferable phthalic acid diester derivatives are compounds having thestructure of the formula (1), wherein n=1 or 2, R¹ is an alkyl groupwith 1 to 5 carbon atoms or a halogen atom, and R² and R³ are alkylgroups with 4 to 8 carbon atoms including a tertiary carbon atom.

Specific examples of the compounds of the above formula (1), wherein n=1or 2, R¹ is an alkyl group with 1 to 5 carbon atoms or a halogen atom,and R² and R³ are alkyl groups with 4 to 8 carbon atoms including atertiary carbon atom, include dineopentyl 3-methylphthalate, dineopentyl4-methylphthalate, dineopentyl 3-ethylphthalate, dineopentyl4-ethylphthalate, t-butylneopentyl 3-methylphthalate, t-butylneopentyl4-methylphthalate, t-butyl neopentyl 3-ethylphthalate, t-butylneopentyl4-ethylphthalate, dineopentyl 4,5-dimethyl phthalate, dineopentyl4,5-diethyl phthalate, t-butyl dineopentyl 4,5-dimethylphthalate,t-butyl neopentyl 4,5-diethylphthalate,dineopentyl 3-fluorophthalate,dineopentyl 3-chlorophthalate, dineopentyl 4-chlorophthalate,dineopentyl 4-bromophthalate, and dineopentyl 4-t-butyl phthalate. Ofthese compounds dineopentyl 4-methylphthalate, dineopentyl4,5-dimethylphthalate, dineopentyl 4-ethyl phthalate, dineopentyl4,5-diethylphthalate, dineopentyl 4-bromophthalate, dineopentyl3-fluorophthalate, and dineopentyl 4-t-butylphthalate are particularlypreferable.

Specific examples of the compounds of the above formula (1), whereinn=2, one of the groups R¹ is a halogen atom and the other is an alkylgroup with 1 to 8 carbon atoms, and at least one of the groups R² and R³is an alkyl group with 1 to 12 carbon atoms other than the alkyl groupwith 4 to 8 carbon atoms including a tertiary carbon atom include:diethyl 4-methyl-5-chlorophthalate, diethyl 4-methyl-5-bromo phthalate,diethyl 4-ethyl-5-chlorophthalate, diethyl 4-ethyl-5-bromophthalate,di-n-butyl 4-methyl-5-chlorophthalate, di-n-butyl4-methyl-5-bromophthalate, di-n-butyl 4-ethyl-5-chlorophthalate,di-n-butyl 4-ethyl-5-bromophthalate, diisobutyl4-methyl-5-chlorophthalate, diisobutyl 4-methyl-5-bromophthalate,diisobutyl 4-ethyl-5-chloro phthalate, diisobutyl4-ethyl-5-bromophthalate, diisohexyl 4-methyl-5-chlorophthalate,diisohexyl 4-methyl-5-bromo phthalate, diisohexyl4-ethyl-5-chlorophthalate, diisohexyl 4-ethyl-5-bromophthalate,diisooctyl 4-methyl-5-chloro phthalate, diisooctyl4-methyl-5-bromophthalate, diisooctyl 4-ethyl-5-chlorophthalate,diisooctyl 4-ethyl-5-bromo phthalate, ethyl-n-butyl4-methyl-5-chlorophthalate, ethyl-n-butyl 4-chloro-5-methyl phthalate,ethyl-n-butyl 4-methyl-5-bromophthalate, ethyl-n-butyl 4-bromo-5-methylphthalate, ethyl-n-butyl 4-ethyl-5-chlorophthalate, ethyl-n-butyl4-chloro-5-ethylphthalate, ethyl-n-butyl 4-ethyl-5-bromo phthalate,ethyl-n-butyl 4-bromo-5-ethylphthalate, ethyl isobutyl4-methyl-5-chlorophthalate, ethylisobutyl 4-chloro-5-methylphthalate,ethylisobutyl 4-methyl-5-bromo phthalate, ethylisobutyl4-bromo-5-methylphthalate, ethyl isobutyl 4-ethyl-5-chlorophthalate,ethyl isobutyl 4-chloro-5-ethylphthalate, ethylisobutyl4-ethyl-5-bromophthalate, ethylisobutyl 4-bromo-5-ethylphthalate,ethylisohexyl 4-methyl-5-chlorophthalate, ethylisohexyl4-chloro-5-methylphthalate, ethylisohexyl 4-methyl-5-bromophthalate,ethylisohexyl 4-bromo-5-methylphthalate, ethylisohexyl4-ethyl-5-chlorophthalate, ethylisohexyl 4-chloro-5-ethyl phthalate,ethylisohexyl 4-ethyl-5-bromophthalate, ethyl isohexyl4-bromo-5-ethylphthalate, n-butylisobutyl 4-methyl-5-chlorophthalate,n-butylisobutyl 4-chloro-5-methyl phthalate, n-butylisobutyl4-methyl-5-bromophthalate, n-butylisobutyl 4-bromo-5-methyl phthalate,n-butylisobutyl 4-ethyl-5-chlorophthalate, n-butyl isobutyl4-chloro-5-ethylphthalate, n-butylisobutyl 4-ethyl-5-bromophthalate,n-butylisobutyl 4-bromo-5-ethylphthalate, n-butylisohexyl4-methyl-5-chlorophthalate, n-butylisohexyl 4-chloro-5-methylphthalate,n-butylisohexyl 4-methyl-5-bromo phthalate, n-butylisohexyl4-bromo-5-methylphthalate, n-butyl isohexyl 4-ethyl-5-chlorophthalate,n-butylisohexyl 4-chloro-5-ethylphthalate, n-butylisohexyl4-ethyl-5-bromophthalate, and n-butylisohexyl 4-bromo-5-ethylphthalate.

Specific examples of the compounds of the above formula (1), wherein n=1or 2, R¹ is an alkyl group with 1 to 8 carbon atoms, and R² and R³ arealkyl groups with 1 to 12 carbon atoms other than the alkyl group with 4to 8 carbon atoms including a tertiary carbon atom include diethyl3-methylphthalate, diethyl 4-methylphthalate, diethyl 3-ethylphthalate,diethyl 4-ethylphthalate, diethyl 3-t-butylphthalate, diethyl 4-t-butylphthalate, diethyl 3-n-butylphthalate, diethyl 4-n-butylphthalate,diethyl 4,5-dimethylphthalate, diethyl 4,5-diethylphthalate, diethyl4-methyl-5-ethylphthalate, diethyl 4-methyl-5-t-butylphthalate, diethyl4-ethyl-5-t-butylphthalate, di-n-butyl 3-methylphthalate, di-n-butyl4-methylphthalate, di-n-butyl 3-ethylphthalate, di-n-butyl4-ethylphthalate, di-n-butyl 3-t-butylphthalate, di-n-butyl4-t-butylphthalate, di-n-butyl 3-n-butylphthalate, di-n-butyl4-n-butylphthalate, di-n-butyl 4,5-dimethylphthalate, di-n-butyl4,5-diethylphthalate, di-n-butyl 4-methyl-5-ethyl phthalate, di-n-butyl4-methyl-5-t-butylphthalate, di-n-butyl 4-ethyl-5-t-butylphthalate,diisobutyl 3-methyl phthalate, diisobutyl 4-methylphthalate, diisobutyl3-ethyl phthalate, diisobutyl 4-ethylphthalate, diisobutyl 3-t-butylphthalate, diisobutyl 4-t-butylphthalate, diisobutyl 3-n-butylphthalate,diisobutyl 4-n-butylphthalate, diisobutyl4,5-dimethylphthalate,-diisobutyl 4,5-diethylphthalate, diisobutyl4-methyl-5-ethylphthalate, diisobutyl 4-methyl-5-t-butylphthalate,diisobutyl 4-ethyl-5-t-butylphthalate, diisohexyl 3-methylphthalate,diisohexyl 4-methylphthalate, diisohexyl 3-ethylphthalate, diisohexyl4-ethylphthalate, diisohexyl 3-t-butylphthalate, diisohexyl4-t-butylphthalate, diisohexyl 3-n-butylphthalate, diisohexyl4-n-butylphthalate, diisohexyl 4,5-dimethylphthalate, diisohexyl4,5-diethyl phthalate, diisohexyl 4-methyl-5-ethylphthalate, diisohexyl4-methyl-5-t-butylphthalate, diisohexyl 4-ethyl-5-t-butyl phthalate,diisooctyl 3-methylphthalate, diisooctyl 4-methyl phthalate, diisooctyl3-ethylphthalate, diisooctyl 4-ethyl phthalate, diisooctyl3-t-butylphthalate, diisooctyl 4-t-butylphthalate, diisooctyl3-n-butylphthalate, diisooctyl 4-n-butylphthalate, diisooctyl4,5-dimethylphthalate, diisooctyl 4,5-diethylphthalate, diisooctyl4-methyl-5-ethyl phthalate, diisooctyl 4-methyl-5-t-butylphthalate,diisooctyl 4-ethyl-5-t-butylphthalate, di-n-decyl 4-methyl phthalate,diisodecyl 4-methylphthalate, di-n-decyl 4-ethyl phthalate, diisodecyl4-ethylphthalate, ethyl-n-butyl 3-methylphthalate, ethyl-n-butyl4-methylphthalate, ethyl-n-butyl 3-ethylphthalate, ethyl-n-butyl4-ethylphthalate, ethyl-n-butyl 3-t-butylphthalate, ethyl-n-butyl4-t-butyl phthalate, ethyl-n-butyl 4,5-dimethylphthalate, ethyl-n-butyl4,5-diethylphthalate, ethyl-n-butyl 4-methyl-5-ethylphthalate,ethyl-n-butyl 4-ethyl-5-methylphthalate, ethylisobutyl3-methylphthalate, ethylisobutyl 4-methyl phthalate, ethylisobutyl3-ethylphthalate, ethylisobutyl 4-ethyl phthalate, ethylisobutyl3-t-butylphthalate, ethyl isobutyl 4-t-butylphthalate, ethylisobutyl4,5-dimethyl phthalate, ethyl isobutyl 4,5-diethylphthalate, ethylisobutyl 4-methyl-5-ethylphthalate, ethylisobutyl4-ethyl-5-methylphthalate, ethylisohexyl 3-methylphthalate, ethylisohexyl 4-methylphthalate, ethylisohexyl 3-ethylphthalate,ethylisohexyl 4-ethylphthalate, ethylisohexyl 3-t-butyl phthalate,ethylisohexyl 4-t-butylphthalate, ethylisohexyl 4,5-dimethylphthalate,ethylisohexyl 4,5-diethylphthalate, ethylisohexyl4-methyl-5-ethylphthalate, ethylisohexyl 4-ethyl-5-methylphthalate,n-butylisobutyl 3-methyl phthalate, n-butylisobutyl 4-methylphthalate,n-butyl isobutyl 3-ethylphthalate, n-butylisobutyl 4-ethylphthalate,n-butylisobutyl 3-t-butylphthalate, n-butylisobutyl 4-t-butylphthalate,n-butylisobutyl 4,5-dimethylphthalate, n-butylisobutyl4,5-diethylphthalate, n-butylisobutyl 4-methyl-5-ethylphthalate,n-butylisobutyl 4-ethyl-5-methyl phthalate, n-butylisohexyl3-methylphthalate, n-butyl isohexyl 4-methylphthalate, n-butylisohexyl3-ethylphthalate, n-butylisohexyl 4-ethylphthalate, n-butylisohexyl3-t-butyl phthalate, n-butylisohexyl 4-t-butylphthalate, n-butylisohexyl 4,5-dimethylphthalate, n-butylisohexyl 4,5-diethyl phthalate,n-butylisohexyl 4-methyl-5-ethylphthalate, and n-butyl isohexyl4-ethyl-5-methylphthalate.

Specific examples of the compounds of the above formula (1), wherein n=1and R¹ is an alkyl group with 1 to 5 carbon atoms, or n=2 and R¹ is analkyl group with 1 to 5 carbon atoms or a halogen atom, and one of thegroups R² and R³ is an alkyl group with 4 to 8 carbon atoms including atertiary carbon atom include ethyl-t-butyl 3-methylphthalate,ethyl-t-butyl 4-methylphthalate, ethyl-t-butyl 3-ethylphthalate,ethyl-t-butyl 4-ethylphthalate, ethyl-t-butyl 4,5-dimethyl phthalate,ethyl-t-butyl 4,5-diethylphthalate, ethyl-t-butyl4-methyl-5-ethylphthalate, ethyl-t-butyl 4-ethyl-5-methylphthalate,ethyl-t-butyl 4-methyl-5-chloro phthalate, ethyl-t-butyl4-chloro-5-methylphthalate, ethyl-t-butyl 4-methyl-5-bromophthalate,ethyl-t-butyl 4-bromo-5-methylphthalate, ethyl-t-butyl 4-ethyl-5-chlorophthalate, ethyl-t-butyl 4-chloro-5-ethylphthalate, ethyl-t-butyl4-ethyl-5-bromophthalate, ethyl-t-butyl 4-bromo-5-ethylphthalate, ethylneopentyl 3-methylphthalate, ethylneopentyl 4-methylphthalate,ethylneopentyl 3-ethyl phthalate, ethylneopentyl 4-ethylphthalate,ethylneopentyl 4,5-dimethylphthalate, ethylneopentyl4,5-diethylphthalate, ethylneopentyl 4-methyl-5-ethylphthalate,ethylneopentyl 4-ethyl-5-methylphthalate, ethylneopentyl4-methyl-5-chlorophthalate, ethylneopentyl 4-chloro-5-methylphthalate,ethylneopentyl 4-methyl-5-bromophthalate, ethylneopentyl4-bromo-5-methylphthalate, ethylneopentyl 4-ethyl-5-chloro phthalate,ethylneopentyl 4-chloro-5-ethylphthalate, ethyl neopentyl4-ethyl-5-bromophthalate, ethylneopentyl 4-bromo-5-ethylphthalate,n-butylneopentyl 3-methylphthalate, n-butylneopentyl 4-methylphthalate,n-butylneopentyl 3-ethylphthalate, n-butylneopentyl 4-ethylphthalate,n-butylneopentyl 4,5-dimethylphthalate, n-butylneopentyl4,5-diethylphthalate, n-butylneopentyl 4-methyl-5-ethyl phthalate,n-butylneopentyl 4-ethyl-5-methylphthalate, n-butylneopentyl4-methyl-5-clilorophthalate, n-butyl neopentyl4-chloro-5-methylphthalate, n-butylneopentyl 4-methyl-5-bromo phthalate,n-butylneopentyl 4-bromo-5-methylphthalate, n-butyl neopentyl4-ethyl-5-chloro phthalate, n-butylneopentyl 4-chloro-5-ethylphthalate,n-butylneopentyl 4-ethyl-5-bromophthalate, and n-butyl neopentyl4-bromo-5-ethylphthalate.

Specific examples of the compounds of the above formula (1), wherein n=1or 2, R¹ is an alkyl group with 6 to 8 carbon atoms, and both R² and R³are alkyl groups with 4 to 8 carbon atoms including a tertiary carbonatom include di-t-butyl 4-n-hexylphthalate, di-t-butyl4-isohexylphthalate, di-t-butyl 4-(2,2-dimethylbutyl)phthalate,di-t-butyl 4-(2,2-dimethylpentyl)phthalate, di-t-butyl isooctylphthalate, di-t-butyl 4-n-hexyl-5-chlorophthalate, di-t-butyl4-n-hexyl-5-bromophthalate, di-t-butyl 4-isohexyl-5-chlorophthalate,di-t-butyl 4-isohexyl-5-bromophthalate, di-t-butyl4-(2,2-dimethylbutyl)-5-chlorophthalate, di-t-butyl4-(2,2-dimethylbutyl)-5-bromophthalate, di-t-butyl 4-(2,2-dimethylpentyl) phthalate, di-t-butyl isooctylphthalate, dineopentyl4-n-hexylphthalate, dineopentyl 4-isohexylphthalate, dineopentyl4-(2,2-dimethylbutyl)phthalate, dineopentyl4-(2,2-dimethylpentyl)phthalate, dineopentyl isooctyl phthalate,dineopentyl 4-n-hexyl-5-chlorophthalate, dineopentyl4-n-hexyl-5-bromophthalate, dineopentyl 4-isohexyl-5-chlorophthalate,dineopentyl 4-isohexyl-5-bromophthalate, dineopentyl4-(2,2-dimethylbutyl)-5-chlorophthalate, dineopentyl4-(2,2-dimethylbutyl)-5-bromophthalate, dineopentyl4-(2,2-dimethylpentyl) phthalate, and dineopentyl isooctylphthalate.

Of these, preferable compounds are diethyl 4-methyl phthalate,di-n-butyl 4-methylphthalate, diisobutyl 4-methyl phthalate, diisohexyl4-methylphthalate, diisooctyl 4-methyl phthalate, diethyl4-ethylphthalate, di-n-butyl 4-ethyl phthalate, diisobutyl4-ethylphthalate, diisohexyl 4-ethyl phthalate, diisooctyl4-ethylphthalate, diethyl 4-t-butyl phthalate, di-n-butyl4-t-butylphthalate, diisobutyl 4-t-butyl phthalate, diisohexyl4-t-butylphthalate, diisooctyl 4-t-butylphthalate, diethyl4,5-dimethylphthalate, di-n-butyl 4,5-dimethylphthalate, diisohexyl4,5-dimethyl phthalate, diisooctyl 4,5-dimethylphthalate, diethyl4,5-diethylphthalate, di-n-butyl 4,5-diethylphthalate, diisohexyl4,5-diethylphthalate, diisooctyl 4,5-diethyl phthalate, diethyl4-methyl-5-chlorophthalate, diethyl 4-methyl-5-bromophthalate, diethyl4-ethyl-5-chloro phthalate, diethyl 4-ethyl-5-bromophthalate, di-n-butyl4-methyl-5-chlorophthalate, di-n-butyl 4-methyl-5-bromo phthalate,di-n-butyl 4-ethyl-5-chlorophthalate, di-n-butyl4-ethyl-5-bromophthalate, diisobutyl 4-methyl-5-chlorophthalate,diisobutyl 4-methyl-5-chlorophthalate, diisobutyl4-methyl-5-bromophthalate, diisobutyl 4-ethyl-5-chlorophthalate,diisobutyl 4-ethyl-5-bromophthalate, diisohexyl4-methyl-5-chlorophthalate, diisohexyl 4-methyl-5-bromophthalate,diisohexyl 4-ethyl-5-chlorophthalate, diisohexyl4-ethyl-5-bromophthalate, diisooctyl 4-methyl-5-chlorophthalate,diisooctyl 4-methyl-5-bromophthalate, diisooctyl 4-ethyl-5-chlorophthalate, diisooctyl 4-ethyl-5-bromophthalate, and the like.

Specific examples of the compounds of the above formula (1), wherein n=1or 2, R¹ is a halogen atom, and at least one of the groups R² or R³ isan alkyl group with 1 to 12 carbon atoms other than the alkyl group with4 to 8 carbon atoms including a tertiary carbon atom include diethyl3-fluoro phthalate, diethyl 4-fluoro phthalate, diethyl 3-chlorophthalate, diethyl 4-chlorophthalate, diethyl 3-bromo phthalate, diethyl4-bromophthalate, diethyl 3-iodophthalate, diethyl 4-iodophthalate,diethyl 4,5-dichloro phthalate, diethyl 4,5-dibromophthalate, diethyl4-chloro-5-bromo phthalate, di-n-butyl 3-fluorophthalate, di-n-butyl4-fluorophthalate, di-n-butyl 3-chlorophthalate, di-n-butyl4-chlorophthalate, di-n-butyl 3-bromophthalate, di-n-butyl4-bromophthalate, di-n-butyl 3-iodophthalate, di-n-butyl4-iodophthalate, di-n-butyl 4,5-dichlorophthalate, di-n-butyl4,5-dibromophthalate, di-n-butyl 4-chloro-5-bromo phthalate, diisobutyl3-fluorophthalate, diisobutyl 4-fluorophthalate, diisobutyl3-chlorophthalate, diisobutyl 4-chlorophthalate, diisobutyl3-bromophthalate, diisobutyl 4-bromophthalate, diisobutyl3-iodophthalate, diisobutyl 4-iodophthalate, diisobutyl4,5-dichlorophthalate, diisobutyl 4,5-dibromophthalate, diisobutyl4-chloro-5-bromophthalate, diisohexyl 3-fluorophthalate, diisohexyl4-fluorophthalate, diisohexyl 3-chlorophthalate, diisohexyl4-chlorophthalate, diisohexyl 3-bromophthalate, diisohexyl4-bromophthalate, diisohexyl 3-iodophthalate, diisohexyl4-iodophthalate, isohexyl 4,5-dichlorophthalate, diisohexyl4,5-dibromophthalate, diisohexyl 4-chloro-5-bromophthalate, diisooctyl3-fluorophthalate, diisooctyl 4-fluorophthalate, diisooctyl3-chlorophthalate, diisooctyl 4-chlorophthalate, diisooctyl3-bromophthalate, diisooctyl 4-bromophthalate, diisooctyl3-iodophthalate, diisooctyl 4-iodophthalate, diisooctyl4,5-dichlorophthalate, diisooctyl 4,5-dibromophthalate, diisooctyl4-chloro-5-bromo phthalate, di-n-decyl 4-chlorophthalate, isodecyl4-chloro phthalate, di-n-decyl 4-bromophthalate, isodecyl 4-bromophthalate, ethyl-n-butyl 3-fluorophthalate, ethyl-n-butyl4-fluorophthalate, ethyl-n-butyl 3-chlorophthalate, ethyl-n-butyl4-chlorophthalate, ethyl-n-butyl 3-bromophthalate, ethyl-n-butyl4-bromophthalate, ethyl-n-butyl 3-iodo phthalate, ethyl-n-butyl4-iodophthalate, ethyl-n-butyl 4,5-dichlorophthalate, ethyl-n-butyl4,5-dibromophthalate, ethyl-n-butyl 4-chloro-5-bromophthalate,ethylisobutyl 3-fluorophthalate, ethylisobutyl 4-fluorophthalate,ethylisobutyl 3-chlorophthalate, ethylisobutyl 4-chloro phthalate,ethylisobutyl 3-bromophthalate, ethylisobutyl 4-bromophthalate,ethylisobutyl 3-iodophthalate, ethyl isobutyl 4-iodophthalate,ethylisobutyl 4,5-dichloro phthalate, ethylisobutyl4,5-dibromophthalate, ethyl isobutyl 4-chloro-5-bromophthalate,ethylisohexyl 3-fluorophthalate, ethylisohexyl 4-fluorophthalate, ethylisohexyl 3-chlorophthalate, ethylisohexyl 4-chlorophthalate,ethylisohexyl 3-bromophthalate, ethylisohexyl 4-bromo phthalate,ethylisohexyl 3-iodophthalate, ethylisohexyl 4-iodophthalate,ethylisohexyl 4,5-dichlorophthalate, ethyl isohexyl4,5-dibromophthalate, ethylisohexyl 4-chloro-5-bromophthalate,ethylisobutyl 3-fluorophthalate, ethyl isobutyl 4-fluorophthalate,ethylisobutyl 3-chlorophthalate, ethylisobutyl 4-chlorophthalate,ethylisobutyl 3-bromo phthalate, ethylisobutyl 4-bromophthalate,ethylisobutyl 3-iodophthalate, ethylisobutyl 4-iodophthalate, ethylisobutyl 4,5-dichlorophthalate, ethylisobutyl 4,5-dibromo phthalate,ethylisobutyl 4-chloro-5-bromophthalate, n-butyl isobutyl3-fluorophthalate, n-butylisobutyl 4-fluoro phthalate, n-butylisobutyl3-chlorophthalate, n-butyl isobutyl 4-chlorophthalate, n-butyl isobutyl3-bromophthalate, n-butylisobutyl 4-bromophthalate, n-butylisobutyl3-iodo phthalate, n-butylisobutyl 4-iodophthalate, n-butylisobutyl4,5-dichlorophthalate, n-butylisobutyl 4,5-dibromophthalate,n-butylisobutyl 4-chloro-5-bromophthalate, n-butylisohexyl3-fluorophthalate, n-butylisohexyl 4-fluorophthalate, n-butylisohexyl3-chlorophthalate, n-butylisohexyl 4-chlorophthalate, n-butylisohexyl3-bromophthalate, n-butyl isohexyl 4-bromophthalate, n-butylisohexyl3-iodophthalate, n-butylisohexyl 4-iodophthalate, n-butylisohexyl4,5-dichlorophthalate, n-butylisohexyl 4,5-dibromophthalate,n-butylisohexyl 4-chloro-5-bromophthalate, ethyl-t-butyl3-fluorophthalate, ethyl-t-butyl 4-fluorophthalate, ethyl-t-butyl3-chlorophthalate, ethyl-t-butyl 4-chloro phthalate, ethyl-t-butyl3-bromophthalate, ethyl-t-butyl 4-bromophthalate, ethyl-t-butyl3-iodophthalate, ethyl-t-butyl 4-iodophthalate, ethyl-t-butyl4,5-dichlorophthalate, ethyl-t-butyl 4,5-dibromophthalate, ethyl-t-butyl4-chloro-5-bromophthalate, ethylneopentyl 3-fluorophthalate, ethylneopentyl 4-fluorophthalate, ethylneopentyl 3-chloro phthalate, ethylneopentyl 4-chlorophthalate, ethylneopentyl 3-bromophthalate,ethylneopentyl 4-bromophthalate, ethyl neopentyl 3-iodophthalate,ethylneopentyl 4-iodophthalate, ethylneopentyl 4,5-dichloro phthalate,ethylneopentyl 4,5-dibromophthalate, ethylneopentyl 4-chloro-5-bromophthalate, n-butyl-t-butyl 3-fluorophthalate, n-butyl-t-butyl4-fluorophthalate, n-butyl-t-butyl 3-chlorophthalate, n-butyl-t-butyl4-chlorophthalate, n-butyl-t-butyl 3-bromo phthalate, n-butyl-t-butyl4-bromophthalate, n-butyl-t-butyl 3-iodophthalate, n-butyl-t-butyl4-iodophthalate, n-butyl-t-butyl 4,5-dichlorophthalate, n-butyl-t-butyl4,5-dibromo phthalate, n-butyl-t-butyl 4-chloro-5-bromophthalate,n-butylneopentyl 3-fluorophthalate, n-butylneopentyl 4-fluorophthalate,n-butylneopentyl 3-chlorophthalate, n-butylneopentyl 4-chlorophthalate,n-butylneopentyl 3-bromophthalate, n-butylneopentyl 4-bromophthalate,n-butyl neopentyl 3-iodophthalate, n-butylneopentyl 4-iodophthalate,n-butylneopentyl 4,5-dichlorophthalate, n-butylneopentyl4,5-dibromophthalate, and n-butylneopentyl 4-chloro-5-bromo phthalate.

Of these, preferable compounds are diethyl 4-bromo phthalate, di-n-butyl4-bromophthalate, diisobutyl 4-bromo phthalate, diethyl4-chlorophthalate, di-n-butyl 4-chloro phthalate, diisobutyl4-chlorophthalate, diisohexyl 4-chloro phthalate, diisooctyl4-chlorophthalate, diisohexyl 4-bromo phthalate, diisooctyl4-bromophthalate, diethyl 4,5-dichloro phthalate, di-n-butyl4,5-dichlorophthalate, isohexyl 4,5-dichlorophthalate, and diisooctyl4,5-dichlorophthalate.

Among the above-described phthalic acid diester derivatives,particularly preferred compounds as an electron donor which is one ofthe components of the catalyst for the olefin polymerization aredineopentyl 4-methylphthalate, dineopentyl 3-fluorophthalate,dineopentyl 4,5-dimethyl phthalate, dineopentyl 4-bromophthalate,t-butylneopentyl phthalate, di-n-butyl 4-methylphthalate, di-n-butyl4-t-butyl phthalate, diethyl 4-methylphthalate, diethyl 4-t-butylphthalate, di-n-butyl 4-bromophthalate, di-n-butyl 4-chloro phthalate,di-n-butyl 4,5-dichlorophthalate, diisohexyl 4-bromophthalate, anddineopentyl 4-t-butylphthalate. These phthalic acid diesters derivativesmay be used either individually or in combinations of two or more.

The phthalic acid diester derivatives of the present invention areuseful as an electron donor of various olefin polymerization catalysts.Specifically, these phthalic acid diesters and their derivatives areuseful as an electron donor of catalysts in the homo- orcopolymerization of ethylene, propylene, 1-butene, 1-pentene,4-methyl-1-pentene, vinyl cyclohexane, and the like, preferably in thehomopolymerization of ethylene or propylene, or copolymerization ofethylene and propylene. In particular, these compounds are ideal aselectron donors of catalysts used in the homopolymerization of propyleneor the copolymerization of ethylene and propylene.

The phthalic acid diester derivatives of the present invention can beprepared by various methods. A most simple method is reacting acommercially available phthalate with an alkyl halide, followed byhydrolysis of the resulting product. A number of synthetic methods ofesters are known as described, for example, in “Lecture of ExperimentalChemistry” (the fourth edition, vol. 22). Some examples are describedhere. A most common ester synthetic method comprises an application ofthe dehydration reaction of a carboxylic acid and alcohol. A mineralacid such as hydrochloric acid and sulfuric acid or a base such astriethylamine may be used as a catalyst. Another well-known methodcomprises use of a dehydrating agent for the synthesis of esters. Forexample, dicyclohexyl carbodiimide, trifluoroacetic acid anhydride, andthe like are used as the dehydrating agent. A synthetic method using acarboxylic acid anhydride instead of carboxylic acid is also known.Moreover, a method of synthesizing an ester from an acid halide isknown. This method is commonly used for the esterification of acarboxylic acid with a low reactivity due to steric hindrance, forexample. For synthesis of a carboxylic acid ester of a dibasic acid, amethod of preparing an intermediate such as a mono-ester or half-ester,then obtaining a diester by directly esterifying this intermediate orvia an acid halide is known. These methods and other known methods maybe used.

In a specific synthesis method of dineopentyl 4-methyl phthalate,4-methylphthalic acid and neopentyl alcohol are charged into a flask andrefluxed for 2 hours in the presence of sulfuric acid. After completionof the reaction, the reaction mixture is allowed to cool to the roomtemperature, and distilled water and ether are added to the mixture toextract the reaction product into the ether layer. After repetition of awashing procedure of the ether layer by flushing, an aqueous solution ofsodium hydrogen carbonate is added, followed by neutralization of thewater layer. A salt solution is added and the washing procedure usingdistilled water is repeated. Sodium sulfate is then added to the etherlayer, followed by filtration. Ether contained in the resulting filtrateis removed by vacuum distillation. Vacuum distillation is repeated toobtain a yellow liquid. The liquid is cooled and recrystallized fromethanol to obtain white crystals.

The phthalic acid diester derivative thus obtained can be identified bythe nuclear magnetic resonance spectroscopy (¹H-NMR), Ramanspectrometry, mass spectrometry (MS), and the like.

The use of the phthalic acid diester derivatives of the presentinvention as an electron donor of an olefin polymerization catalystremarkably improves the polymerization activity, the yield of highstereoregularity polymers, and the response to hydrogen of the catalystas compared with conventionally known high performance catalyst.

EXAMPLES

The present invention will be described in more detail by examples,which should not be construed as limiting the present invention.

Example 1

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 25.0 g of 4-methyl phthalate and 100 g of neopentyl alcohol. 18 mlof sulfuric acid was slowly added at 66° C., followed by refluxing fortwo hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 150 ml of distilled water.The flask was washed with 200 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 150 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 300 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 13.0 g of a viscous yellowliquid was obtained at a column top temperature of 190° C. This liquidwas cooled to about −10° C. to obtain white crystals, which wererecrystallized from ethanol to obtain 11.8 g of highly pure whitecrystals (yield: 26.5%). As a result of analysis using the following MSanalyzer, ¹H-NMR analyzer, and Raman spectroscopic analyzer, the whitecrystals were identified to be dineopentyl 4-methyl phthalate. Theresults of the analyses are shown in Tables 1 to 3.

Analyzers

The Finigan Mat (GC-MS) was used for the MS analysis. The JEOL GSX270and a CDCl₃ solvent were used for the ¹H-NMR analysis. The JEOL RFT800was used for the Raman spectroscopic analysis.

Example 2

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 50.0 g of 4-bromophthalate and 100.1 g of neopentyl alcohol. 36 mlof sulfuric acid was slowly added at 69° C., followed by refluxing forthree and a half hours at 115 to 125° C. After cooling, the reactionsolution was transferred to a separating funnel containing 600 ml ofdistilled water. The flask was washed with 500 ml of diethyl ether andthe diethyl ether washing liquid was also poured into the separatingfunnel. After a flushing operation, an operation of removing the waterlayer (lower layer) was repeated three times. After the addition of 250ml of a 5% aqueous solution of sodium hydrogen carbonate, a flushingoperation was carried out to confirm that the water layer has a pH inthe range of 7 to 8. After removing the water layer, the residue waswashed with 300 ml of saturated brine and then with 150 ml of distilledwater. The water layer was removed. The ether layer (upper layer) wastransferred to an Erlenmeyer flask and dehydrated using anhydrous sodiumsulfate. After removal of ether by distillation under reduced pressure,the residue was further distilled under reduced pressure. 61.9 g of aviscous pale yellow liquid was obtained at a column top temperature of170° C. This liquid was cooled to about −10° C. to obtain whitecrystals, which were recrystallized from ethanol to obtain 33.2 g ofhighly pure white crystals (yield: 39.2%). As a result of analysiscarried out in the same manner as above, the white crystals wereidentified to be dineopentyl 4-bromophthalate. The results of theanalyses are shown in Tables 1 to 3.

Example 3

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 24.0 g of 3-fluorophthalate and 99.6 g of neopentyl alcohol. 18 mlof sulfuric acid was slowly added at 62° C., followed by refluxing fortwo hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 300 ml of distilled water.The flask was washed with 210 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 150 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 150 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 15.3 g of a viscous paleyellow liquid was obtained at a column top temperature of 150° C. Thisliquid was crystallized from ethanol to obtain 12.0 g of highly purewhite crystals (yield: 28.4%). As a result of analysis carried out inthe same manner as above, the white crystals were identified to bedineopentyl 3-fluorophthalate. The results of the analyses are shown inTables 1 to 3.

Example 4

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 21.1 g of 4,5-dimethyl phthalate and 99.7 g of neopentyl alcohol.18 ml of sulfuric acid was slowly added at 67° C., followed by refluxingfor two hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 300 ml of distilled water.The flask was washed with 210 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 150 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 150 mlof saturated brine and then with 100 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 18.9 g of a viscous yellowliquid was obtained at a column top temperature of 170° C. This liquidwas crystallized from ethanol to obtain 12.1 g of highly pure whitecrystals (yield: 36.7%). As a result of analysis carried out in the samemanner as above, the white crystals were identified to be dineopentyl4,5-dimethyl phthalate. The results of the analyses are shown in Tables1 to 3.

Example 5

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 32.6 g of 4-tert-butyl phthalate and 150.0 g of neopentyl alcohol.36 ml of sulfuric acid was slowly added at 66° C., followed by refluxingfor three hours at 115 to 125° C. After cooling, the reaction solutionwas transferred to a separating funnel containing 400 ml of distilledwater. The flask was washed with 300 ml of diethyl ether and the diethylether washing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 23.6 g (yield: 44.3%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be dineopentyl 4-tert-butyl phthalate.The results of the analyses are shown in Tables 1 to 3.

Example 6 Preparation of Solid Catalyst Component

A 500 ml round bottom flask equipped with a stirrer, of which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 10 g of diethoxymagnesium and 80 ml toluene to prepare asuspension. After the addition of 20 ml of titanium tetrachloride, thesuspension was heated, and when the temperature increased to as high as80° C., a solution prepared by dissolving 3.5 g of dineopentyl4-methylphthalate obtained in Example 1 in 3.5 ml of toluene was addedand the mixture was heated to 110° C. Then, the mixture was reacted forone hour while stirring at 110° C. After the reaction, the resultingreaction mixture was washed three times with 100 ml of toluene at 90° C.After the addition of 20 ml of titanium tetrachloride and 80 ml oftoluene, the reaction mixture was heated to 110° C. and reacted for onehour while stirring. After the reaction, the resulting reaction mixturewas washed seven times with 100 ml of n-heptane at 40° C., therebyobtaining a solid catalyst component. The liquid in the solid catalystcomponent was separated from the solid components by filtration anddrying. The content of titanium in the solid components was determinedto confirm that the content was 3.7 wt %.

Preparation of Polymerization Catalyst and Polymerization

A 2.0 l autoclave equipped with a stirrer, of which the internalatmosphere had been entirely replaced by nitrogen gas, was charged with1.32 mmol of triethylaluminum, 0.13 mmol ofcyclohexylmethyldimethoxysilane, and the above solid catalyst component(A) in an amount, in terms of the titanium atom contained therein, of0.0026 mmol, thereby forming a polymerization catalyst. Then, with theaddition of 2.0 l of hydrogen gas and 1.4 l of liquid propylene, thepreliminary polymerization was carried out for 5 minutes at 20° C.,following which the preliminary polymerization product was heated andthe main polymerization was carried out for one hour at 70° C. Theweight of the polymer (a) was 270.9 g and the weight of the polymer (b)insoluble in n-heptane determined by extracting this polymer for 6 hoursin boiling n-heptane was 263.0 g. Thus, the proportion of the boilingn-heptane insoluble matters (hereinafter abbreviated as “HI”) in thepolymer was confirmed to be 97.5 wt %. The polymerization activity per 1g of the solid catalyst component used was 60,100 g/g. The melt index(hereinafter abbreviated as “MI”) of the polymer (a), determined by thetest method according to ASTM D1238 or JIS K7210, was 19 g/10 min. Theresults are shown in Table 4. The polymerization activity per 1 g of thesolid catalyst component used here was calculated by the followingformula:

The polymerization activity=(a) 270.9 (g)/solid catalyst component0.00451 (g)

Example 7

A solid catalyst component was prepared in the same manner as in Example6, except for using a solution of 4.2 mg of dineopentyl4-bromophthalate, prepared in Example 2, dissolved in 5.3 ml of tolueneinstead of the solution of 3.5 g of dineopentyl 4-methylphthalate in 3.5ml of toluene. A polymerization catalyst was prepared from the solidcatalyst component and polymerization was carried out using thecatalyst. The content of titanium in the resulting solid catalystcomponent was 2.9 wt %. The polymerization activity of the solidcatalyst component was 60,800 g/g, HI was 97.1 wt %, and MI was 25 g/10min. The results of the polymerization are shown in Table 4.

Example 8

A solid catalyst component was prepared in the same manner as in Example6, except for using a solution of 3.6 mg of dineopentyl3-fluorophthalate, prepared in Example 3, dissolved in 4.7 ml of tolueneinstead of the solution of 3.5 g of dineopentyl 4-methylphthalate in 3.5ml of toluene. A polymerization catalyst was prepared from the solidcatalyst component and polymerization was carried out using thecatalyst. The content of titanium in the resulting solid catalystcomponent was 3.2 wt %. The polymerization activity of the solidcatalyst component was 58,000 g/g, HI was 96.9 wt %, and MI was 18 g/10min. The results of the polymerization are shown in Table 4.

Example 9 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 6

The same experiment as in Example 6 was carried out, except for using1.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 49,400g/g, HI was 98.1 wt %, and MI was 6.6 g/10 min. The results of thepolymerization are shown in Table 4.

Example 10 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 6

The same experiment as in Example 6 was carried out, except for using3.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 60,000g/g, HI was 96.3 wt %, and MI was 40 g/10 min. The results of thepolymerization are shown in Table 4.

Example 11 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 6

The same experiment as in Example 6 was carried out, except for using6.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 62,700g/g, HI was 95.2 wt %, and MI was 140 g/10 min. The results of thepolymerization are shown in Table 4.

Example 12 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 7

The same experiment as in Example 7 was carried out, except for using1.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 50,100g/g, HI was 97.7 wt %, and MI was 9.5 g/10 min. The results of thepolymerization are shown in Table 4.

Example 13 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 7

The same experiment as in Example 7 was carried out, except for using3.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 63,400g/g, HI was 96.2 wt %, and MI was 47 g/10 min. The results of thepolymerization are shown in Table 4.

Example 14 Experiment With a Varied Amount of Hydrogen Using the SolidCatalyst Component of Example 7

The same experiment as in Example 7 was carried out, except for using6.0 l of hydrogen instead of 2.0 l of hydrogen during polymerization.The polymerization activity of the solid catalyst component was 64,700g/g, HI was 94.4 wt %, and MI was 180 g/10 min. The results of thepolymerization are shown in Table 4.

Comparative Example 1

A solid catalyst component was prepared in the same manner as in Example6, except for using 3.3 ml of di-n-pentylphthalate instead of 3.5 g ofdineopentyl 4-methyl phthalate. A polymerization catalyst was preparedfrom the solid catalyst component and polymerization was carried outusing the catalyst. The content of titanium in the resulting solidcatalyst component was 2.6 wt %. The polymerization activity of thesolid catalyst component was 46,400 g/g, HI was 97.9 wt %, and MI was 10g/10 min. The results of the polymerization are shown in Table 4.

Comparative Example 2

A solid catalyst component was prepared in the same manner as in Example6, except for using 2.9 ml of di-n-butylphthalate instead of 3.5 g ofdineopentyl 4-methylphthalate. A polymerization catalyst was preparedfrom the solid catalyst component and polymerization was carried outusing the catalyst. The content of titanium in the resulting solidcatalyst component was 3.0 wt %. The polymerization activity of thesolid catalyst component was 42,400 g/g, HI was 98.7 wt %, and MI was6.6 g/10 min. The results of the polymerization are shown in Table 4.

Comparative Example 3 Experiment With a Varied Amount of Hydrogen Usingthe Solid Catalyst Component of Comparative Example 1

The same experiment as in Comparative Example 1 was carried out, exceptfor using 3.0 l of hydrogen instead of 2.0 l of hydrogen duringpolymerization. The polymerization activity of the solid catalystcomponent was 47,000 g/g, HI was 97.2 wt %, and MI was 24 g/10 min. Theresults of the polymerization are shown in Table 4.

Comparative Example 4 Experiment With a Varied Amount of Hydrogen Usingthe Solid Catalyst Component of Comparative Example 1

The same experiment as in Comparative Example 1 was carried out, exceptfor using 6.0 l of hydrogen instead of 2.0 l of hydrogen duringpolymerization. The polymerization activity of the solid catalystcomponent was 48,200 g/g, HI was 96.8 wt %, and MI was 66 g/10 min. Theresults of the polymerization are shown in Table 4.

Comparative Example 5 Experiment With a Varied Amount of Hydrogen Usingthe Solid Catalyst Component of Comparative Example 2

The same experiment as in Comparative Example 2 was carried out, exceptfor using 3.0 l of hydrogen instead of 2.0 l of hydrogen duringpolymerization. The polymerization activity of the solid catalystcomponent was 44,500 g/g, HI was 97.6 wt %, and MI was 16 g/10 min. Theresults of the polymerization are shown in Table 4.

Comparative Example 6 Experiment With a Varied Amount of Hydrogen Usingthe Solid Catalyst Component of Comparative Example 2

The same experiment as in Comparative Example 2 was carried out, exceptfor using 6.0 l of hydrogen instead of 2.0 l of hydrogen duringpolymerization. The polymerization activity of the solid catalystcomponent was 47,500 g/g, HI was 97.2 wt %, and MI was 57 g/10 min. Theresults of the polymerization are shown in Table 4.

Example 15

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 25.0 g of 4-methyl phthalate and 100 g of n-butyl alcohol. 18 ml ofsulfuric acid was slowly added at 66° C., followed by refluxing for twohours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 150 ml of distilled water.The flask was washed with 200 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 150 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 300 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 13.0 g of a viscous yellowliquid was obtained at a column top temperature of 190° C. This liquidwas cooled to about −10° C. to obtain white crystals, which wererecrystallized from ethanol to obtain 11.8 g of highly pure whitecrystals (yield: 26.5%). As a result of analysis using the following MSanalyzer, ¹H-NMR analyzer, and Raman spectroscopic analyzer, the whitecrystals were identified to be di-n-butyl 4-methyl phthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 16

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 50.0 g of 4-bromophthalate and 100.1 g of n-butyl alcohol. 36 ml ofsulfuric acid was slowly added at 69° C., followed by refluxing forthree and a half hours at 115 to 125° C. After cooling, the reactionsolution was transferred to a separating funnel containing 600 ml ofdistilled water. The flask was washed with 500 ml of diethyl ether andthe diethyl ether washing liquid was also poured into the separatingfunnel. After a flushing operation, an operation of removing the waterlayer (lower layer) was repeated three times. After the addition of 250ml of a 5% aqueous solution of sodium hydrogen carbonate, a flushingoperation was carried out to confirm that the water layer has a pH inthe range of 7 to 8. After removing the water layer, the residue waswashed with 300 ml of saturated brine and then with 150 ml of distilledwater. The water layer was removed. The ether layer (upper layer) wastransferred to an Erlenmeyer flask and dehydrated using anhydrous sodiumsulfate. After removal of ether by distillation under reduced pressure,the residue was further distilled under reduced pressure. 61.9 g of aviscous pale yellow liquid was obtained at a column top temperature of170° C. This liquid was cooled to about −10° C. to obtain whitecrystals, which were recrystallized from ethanol to obtain 33.2 g ofhighly pure white crystals (yield: 39.2%). As a result of analysiscarried out in the same manner as above, the white crystals wereidentified to be di-n-butyl 4-bromophthalate. The results of theanalyses are shown in Tables 1 to 3.

Example 17

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 32.6 g of 4-tert-butyl phthalate and 100.0 g of n-butyl alcohol. 36ml of sulfuric acid was slowly added at 66° C., followed by refluxingfor three hours at 115 to 125° C. After cooling, the reaction solutionwas transferred to a separating funnel containing 400 ml of distilledwater. The flask was washed with 300 ml of diethyl ether and the diethylether washing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 20.5 g (yield: 43.3%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be di-n-butyl 4-t-butylphthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 18

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 25.0 g of 4-methyl phthalate and 100 g of ethyl alcohol. 36 ml ofsulfuric acid was slowly added at 66° C., followed by refluxing forthree hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 400 ml of distilled water.The flask was washed with 300 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 12.5 g (yield: 37.5%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be diethyl 4-methylphthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 19

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 32.6 g of 4-tert-butyl phthalate and 100.0 g of ethyl alcohol. 36ml of sulfuric acid was slowly added at 66° C., followed by refluxingfor three hours at 115 to 125° C. After cooling, the reaction solutionwas transferred to a separating funnel containing 400 ml of distilledwater. The flask was washed with 300 ml of diethyl ether and the diethylether washing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 18.5 g (yield: 45.3%) of aviscous yellow liquid was obtained at a column top temperature of about170° C. As a result of analysis carried out in the same manner as above,the yellow liquid was identified to be diethyl 4-t-butylphthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 20

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 30.0 g of 4-chlorophthalate and 100 g of n-butyl alcohol. 36 ml ofsulfuric acid was slowly added at 66° C., followed by refluxing forthree hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 400 ml of distilled water.The flask was washed with 300 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 18.5 g (yield: 39.1%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be di-n-butyl 4-chlorophthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 21

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 33.0 g of 4,5-dichlorophthalate and 100 g of n-butyl alcohol. 36 mlof sulfuric acid was slowly added at 66° C., followed by refluxing forthree hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 400 ml of distilled water.The flask was washed with 300 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 16.3 g (yield: 33.0%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be di-n-butyl 4,5-dichlorophthalate. Theresults of the analyses are shown in Tables 1 to 3.

Example 22

A 2.0 l three-necked flask equipped with a reflux condenser was chargedwith 50.0 g of 4-bromophthalate and 100 g of isohexyl alcohol. 36 ml ofsulfuric acid was slowly added at 66° C., followed by refluxing forthree hours at 115 to 125° C. After cooling, the reaction solution wastransferred to a separating funnel containing 400 ml of distilled water.The flask was washed with 300 ml of diethyl ether and the diethyl etherwashing liquid was also poured into the separating funnel. After aflushing operation, an operation of removing the water layer (lowerlayer) was repeated three times. After the addition of 200 ml of a 5%aqueous solution of sodium hydrogen carbonate, a flushing operation wascarried out to confirm that the water layer has a pH in the range of 7to 8. After removing the water layer, the residue was washed with 200 mlof saturated brine and then with 150 ml of distilled water. The waterlayer was removed. The ether layer (upper layer) was transferred to anErlenmeyer flask and dehydrated using anhydrous sodium sulfate. Afterremoval of ether by distillation under reduced pressure, the residue wasfurther distilled under reduced pressure. 35.5 g (yield: 42.1%) of aviscous yellow liquid was obtained at a column top temperature of 170°C. As a result of analysis carried out in the same manner as above, theyellow liquid was identified to be diisohexyl 4-bromophthalate. Theresults of the analyses are shown in Tables 1 to 3.

TABLE 1 MS (Mw/z) Molecular Character- Example Compound Name peak isticpeak 1 dineopentyl 4-methylphthalate 320 163 2 dineopentyl4-bromophthalate 384, 386 184, 182 3 dineopentyl 3-fluorophthalate 324167 4 dineopentyl 4,5-dimethylphthalate 334 177 5 dineopentyl4-t-butylphthalate 362 205 15 di-n-butyl 4-methylphthalate 292 163 16di-n-butyl 4-bromophthalate 356, 358 227, 229 17 di-n-butyl4-t-butylphthalate 334 205 18 diethyl 4-methylphthalate 236 163 19diethyl 4-t-butylphthalate 278 205 20 di-n-butyl 4-chlorophthalate 312183 21 di-n-butyl 4,5-dichlorophthalate 346, 348 217 22 diisohexyl4-bromophthalate 412, 414 182, 184

TABLE 2 ¹H-NMR (ppm:Int) Example Compound Name Methyl al Methyl arMethylene Aromatic ring 1 dineopentyl 4-methylphthalate 1.0s:18.12.4s:3.0 4.0s:4.0 7.3-7.7m:3.0 2 dineopentyl 4-bromophthalate 1.0s:18.0— 4.0d:4.0 7.6-7.8m:3.0 3 dineopentyl 3-fluorophthalate 1.0d:18.0 —4.0s:2.0 7.3-7.8m:3.0 4.1s:2.0 4 dineopentyl 1.0s:18.0 2.4s:6.0 4.0s:4.07.6s:2.0 4,5-dimethylphthalate 5 dineopentyl 4-t-butylphthalate1.0d:18.0 — 4.0d:4.0 7.3-7.8m:3.0 1.3s:9.0 15 di-n-butyl4-methylphthalate 1.0t:6.0 2.4s:3.0 1.4q:4.1 7.3-7.8m:3.0 1.7m:4.04.3m:4.0 16 di-n-butyl 4-bromophthalate 1.0td:6.1 — 1.4q:4.17.2-7.8m:2.9 1.7m:4.1 4.3td:4.0 17 di-n-butyl 4-t-butylphthalate1.0t:6.0 — 1.4m:4.0 7.3-7.8m:3.0 1.3s:9.0 1.7m:4.1 4.3t:4.0 18 diethyl4-methylphthalate 1.4t:6.0 2.4s:3.0 4.4q:4.0 7.9s:3.0 19 diethyl4-t-butylphthalate 1.3s:9.0 — 4.4q:4.0 7.3-7.8m:3.0 1.4t:6.0 20di-n-butyl 4-chlorophthalate 1.0t:6.0 — 1.4m:4.0 7.5-7.8m:3.0 1.7m:4.04.3t:4.0 21 di-n-butyl 4,5-dichlorophthalate 1.0t:6.0 — 1.4m:4.07.9s:2.0 1.7m:4.0 4.3t:4.0 22 diisohexyl 4-bromophthalate 0.9d:12.0 —1.0-1.8m:2.1 7.2-7.8m:3.0 1.3m:4.0 1.6m:3.9 3.6t:4.0

TABLE 3 Elemental analysis (%) Raman (cm⁻¹) Found/Theoretical ExampleCompound Name C═O C-Car Cal-H C H O 1 dineopentyl 4-methylphthalate 17241612 2963 71.1/ 8.8/ 20.0/ 2923 71.2 8.8 20.0 2 dineopentyl4-bromophthalate 1730 1593 2962 56.1/ 6.2/ 16.6/ 2940 56.1 6.5 16.6 3dineopentyl 3-fluorophthalate 1728 1610 2960 66.7/ 8.1/ 20.2/ 2908 66.67.8 19.7 4 dineopentyl 1720 1613 2965 71.8/ 8.9/ 19.2/4,5-dimethylphthalate 2927 71.8 9.0 19.1 5 dineopentyl4-t-butylphthalate 1724 1612 2962 72.8/ 9.3/ 17.8/ 2918 72.9 9.5 17.7 15di-n-butyl 4-methylphthalate 1722 1608 2913 69.8/ 8.2/ 20.7/ 2873 69.88.2 21.9 16 di-n-butyl 4-bromophthalate 1724 1589 2976 54.1/ 5.9/ 15.7/2937 53.8 5.9 17.9 17 di-n-butyl 4-t-butylphthalate 1726 1606 2960 71.8/9.0/ 18.9/ 2908 71.8 9.0 19.1 18 diethyl 4-methylphthalate 1722 16102951 66.2/ 6.7/ 27.1/ 2911 66.1 6.8 27.1 19 diethyl 4-t-butylphthalate1724 1606 2968 68.8/ 8.1/ 22.9/ 2937 69.0 8.0 23.0 20 di-n-butyl4-chlorophthalate 1726 1593 2935 60.9/ 6.7/ 19.8/ 2907 61.4 6.8 20.52910 21 di-n-butyl 4,5-dichlorophthalate 1730 1589 2935 55.5/ 5.9/ 18.2/2911 55.3 5.8 18.4 2873 22 diisohexyl 4-bromophthalate 1724 1592 297157.9/ 7.2/ 19.1/ 2940 58.1 7.1 19.3 2871

TABLE 4 Titanium Amount of content Polymerization HI MI Compound Namehydrogen (I) (wt %) activity (wt %) (wt %) (g/10 min.) Example 6dineopentyl 4-methylphthalate 2.0 2.8 60,100 97.5 19 Example 7dineopentyl 4-bromophthalate 2.0 2.9 60,800 97.1 25 Example 8dineopentyl 3-fluorophthalate 2.0 3.2 58,000 96.9 18 Example 9dineopentyl 4-methylphthalate 1.0 2.8 49,400 98.1 6.6 Example 10dineopentyl 4-methylphthalate 3.0 2.8 60,000 96.3 40 Example 11dineopentyl 4-methylphthalate 6.0 2.8 62,700 95.2 140 Example 12dineopentyl 4-bromophthalate 1.0 2.9 50,100 97.7 9.5 Example 13dineopentyl 4-bromophthalate 3.0 2.9 63,400 96.2 47 Example 14dineopentyl 4-bromophthalate 6.0 2.9 64,700 94.4 180 Comparative Example1 di-n-pentyl phthalate 2.0 2.6 46,400 97.9 10 Comparative Example 2di-n-butyl phthalate 2.0 3.0 42,400 98.7 6.6 Comparative Example 3di-n-pentyl phthalate 3.0 2.6 47,000 97.2 24 Comparative Example 4di-n-pentyl phthalate 6.0 2.6 48,200 96.8 66 Comparative Example 5di-n-pentyl phthalate 3.0 3.0 44,500 97.6 16 Comparative Example 6di-n-pentyl phthalate 6.0 3.0 47,500 97.0 57

Example 23 Preparation of Solid Catalyst Component (A)

A 500 ml round bottom flask equipped with a stirrer, of which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 10 g of diethoxy magnesium and 80 ml of toluene to preparea suspension. After the addition of 20 ml of titanium tetrachloride, thesuspension was heated, and when the temperature increased to as high as80° C., 3.2 g of di-n-butyl 4-methylphthalate obtained in Example 15 wasadded and the mixture was heated to 110° C. Then, the mixture wasreacted for one hour while stirring at 110° C. After the reaction, theresulting reaction mixture was washed three times with 100 ml of tolueneat 90° C. After the addition of 20 ml of titanium tetrachloride and 80ml of toluene, the reaction mixture was heated to 110° C. and reactedfor one hour while stirring. After the reaction, the resulting reactionmixture was washed seven times with 100 ml of n-heptane at 40° C.,thereby obtaining a solid catalyst component. The liquid in the solidcatalyst component was separated from the solid components. The contentof titanium in the solid components was determined to confirm that thecontent was 3.2 wt %.

Preparation of Polymerization Catalyst and Polymerization

The polymerization was carried out in the same manner as in Example 6.The results are shown in Table 5.

Example 24

A solid catalyst component was prepared in the same manner as in Example23, except for using 3.7 g of di-n-butyl 4-t-butylphthalate prepared inExample 17 instead of 3.2 g of di-n-butyl 4-methylphthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 3.3 wt %. Theresults of polymerization are also shown in Table 5.

Example 25

A solid catalyst component was prepared in the same manner as in Example23, except for using 2.5 g of diethyl 4-methylphthalate prepared inExample 18 instead of 3.2 g of di-n-butyl 4-methylphthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 3.1 wt %. Theresults of polymerization are also shown in Table 5.

Example 26

A solid catalyst component was prepared in the same manner as in Example23, except for using 3.0 g of diethyl 4-t-butylphthalate prepared inExample 19 instead of 3.2 g of di-n-butyl 4-methylphthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 3.4 wt %. Theresults of polymerization are also shown in Table 5.

Example 27

Using a solid catalyst component obtained in the same manner as inExample 23, a polymerization catalyst was prepared in the same manner asin Example 6, except that 0.13 mmol of dicyclopentyldimethoxysilane(DCPDMS) was used as an organic silicon compound instead of 0.13 mmol ofthe cyclohexylmethyldimethoxysilane (CMDMS). The results ofpolymerization are also shown in Table 5.

Example 28

Using a solid catalyst component obtained in the same manner as inExample 23, a polymerization catalyst was prepared in the same manner asin Example 6, except that 0.13 mmol of diisopropyldimethoxysilane(DCPDMS) was used as an organic silicon compound instead of 0.13 mmol ofthe cyclohexylmethyldimethoxysilane (CMDMS). The results ofpolymerization are also shown in Table 5.

Comparative Example 7

Using a solid catalyst component obtained in the same manner as inComparative Example 2, a polymerization catalyst was prepared in thesame manner as in Comparative Example 1, except that 0.13 mmol ofdicyclopentyldimethoxysilane (DCPDMS) was used as an organic siliconcompound instead of 0.13 mmol of the cyclohexylmethyldimethoxysilane(CMDMS). The results of polymerization are also shown in Table 5.

Comparative Example 8

Using a solid catalyst component obtained in the same manner as inComparative Example 2, a polymerization catalyst was prepared in thesame manner as in Comparative Example 1, except that 0.13 mmol ofdiisopropyldimethoxysilane (DCPDMS) was used as an organic siliconcompound instead of 0.13 mmol of the cyclohexylmethyldimethoxysilane(CMDMS). The results of polymerization are also shown in Table 5.

TABLE 5 Polymerization MI Organic activity HI (g/10 silicon (g/g-cat.)(wt %) min) compound Example 23 50,300 98.6 14 CMDMS Example 24 47,20098.0 17 CMDMS Example 25 52,000 98.9 13 CMDMS Example 26 47,900 98.3 13CMDMS Example 27 57,100 99.1 7.0 DCPDMS Example 28 53,200 98.9 11 DIPDMSComparative Example 7 52,900 99.1 3.6 DCPDMS Comparative Example 847,500 98.7 6.8 DIPDMS

Example 29 Preparation of Solid Catalyst Component (A)

A 500 ml round bottom flask equipped with a stirrer, of which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 10 g of diethoxymagnesium and 80 ml toluene to prepare asuspension. After the addition of 20 ml of titanium tetrachloride, thesuspension was heated, and when the temperature increased to as high as80° C., 3.9 g of di-n-butyl 4-bromophthalate obtained in Example 16 wasadded and the mixture was heated to 110° C. Then, the mixture wasreacted for one hour while stirring at 110° C. After the reaction, theresulting reaction mixture was washed three times with 100 ml of tolueneat 90° C. After the addition of 20 ml of titanium tetrachloride and 80ml of toluene, the reaction mixture was heated to 110° C. and reactedfor one hour while stirring. After the reaction, the resulting reactionmixture was washed seven times with 100 ml of n-heptane at 40° C.,thereby obtaining a solid catalyst component. The liquid in the solidcatalyst component was separated from the solid components. The contentof titanium in the solid components was determined to confirm that thecontent was 2.6 wt %.

Preparation of Polymerization Catalyst and Polymerization

The polymerization was carried out in the same manner as in Example 6.The results are shown in Table 6.

Example 30

A solid catalyst component was prepared in the same manner as in Example1, except for using 3.2 g of di-n-butyl 4-chlorophthalate prepared inExample 20 instead of 3.9 g of di-n-butyl 4-bromophthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 3.3 wt %. Theresults of polymerization are also shown in Table 6.

Example 31

A solid catalyst component was prepared in the same manner as in Example1, except for using 3.8 g of di-n-butyl 4,5-dichlorophthalate preparedin Example 21 instead of 3.9 g of di-n-butyl 4-bromophthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 3.0 wt %. Theresults of polymerization are also shown in Table 6.

Example 32

A solid catalyst component was prepared in the same manner as in Example1, except for using 4.5 g of diisohexyl 4-bromophthalate prepared inExample 22 instead of 3.9 g of di-n-butyl 4-bromophthalate. Apolymerization catalyst was prepared from the solid catalyst componentand polymerization was carried out using the catalyst. The content oftitanium in the resulting solid catalyst component was 2.9 wt %. Theresults of polymerization are also shown in Table 6.

Example 33

Using a solid catalyst component obtained in the same manner as inExample 29, a polymerization catalyst was prepared in the same manner asin Example 6, except that 0.13 mmol of dicyclopentyldimethoxysilane(DCPDMS) was used as an organic silicon compound instead of 0.13 mmol ofthe cyclohexylmethyldimethoxysilane (CMDMS). The results ofpolymerization are also shown in Table 6.

Example 34

Using a solid catalyst component obtained in the same manner as inExample 29, a polymerization catalyst was prepared in the same manner asin Example 6, except that 0.13 mmol of diisopropyldimethoxysilane(DCPDMS) was used as an organic silicon compound instead of 0.13 mmol ofthe cyclohexylmethyldimethoxysilane (CMDMS). The results ofpolymerization are also shown in Table 6.

TABLE 6 Polymerization HI MI Organic silicon activity (g/g-cat.) (Wt %)(g/10 min) compound Example 29 49,800 98.5 13 CMDMS Example 30 47,20098.2 15 CMDMS Example 31 43,900 97.9 21 CMDMS Example 32 49,400 98.0 18CMDMS Example 33 54,400 99.0 7.5 DCPDMS Example 34 53,500 98.8 12 DIPDMS

As can be seen from the results of Tables 4, 5, and 6, olefin polymerscan be obtained at an extremely high yield by polymerizing olefins usingthe catalyst containing the phthalic acid diester derivatives of thepresent invention as an electron donor. In addition, the polymers of theExamples have a higher MI value as compared with the polymers of theComparative Examples, indicating a higher response to hydrogen of thecatalyst.

INDUSTRIAL APPLICABILITY

As mentioned above, the phthalic acid diester derivatives of the presentinvention remarkably improves the polymerization activity, increases theyield of high stereoregularity polymers, and promotes the response tohydrogen of the catalyst if used as an electron donor of an olefinpolymerization catalyst as compared with conventionally known highperformance catalyst. The catalyst is thus expected not only to producepolyolefins for common use at a low cost, but also to be useful in themanufacture of copolymer olefins having high functions.

What is claimed is:
 1. A phthalic acid diester derivative of thefollowing formula (1),

wherein R¹ is an alkyl group having 1 to 8 carbon atoms or a halogenatom; R² and R³ may be either identical or different, representing analkyl group having 1 to 12 carbon atoms; and n, which indicates thenumber of R¹, is 1 or 2, provided that when n is 2, the two groups maybe either identical or different, provided further that at least one ofthe groups or R³ is an alkyl group having a tertiary carbon atom andcontaining 4 to 8 carbon atoms.
 2. The phthalic acid diester derivativeaccording to claim 1, having the formula (1) wherein n=1 and R¹ is amethyl group or a tert-butyl group, or n=2 and at least one of thegroups R¹ is a methyl group or a tert-butyl group.
 3. The phthalic aciddiester derivative according to claim 1, having the formula (1) whereinR¹ is a chlorine atom, a bromine atom, or a fluorine atom.
 4. Thephthalic acid diester derivative according to claim 1, having theformula (1) wherein the group R¹ replaces the hydrogen atom at least oneof the 4 and 5 positions of the benzene ring.
 5. The phthalic aciddiester derivative according to claim 1, having the formula (1) whereinat least one of the groups R² or R³ is a neopentyl group or a tert-butylgroup.
 6. The phthalic acid diester derivative according to claim 1,wherein the phthalic acid diester derivative is dineopentyl4-methylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl4-bromophthalate, dineopentyl 3-fluorophthalate, or dineopentyl4-t-butyl phthalate.
 7. The phthalic acid diester derivative accordingto claim 1, wherein R² is a neopentyl group.
 8. The phthalic aciddiester derivative according to claim 1, wherein R³ is a neopentylgroup.
 9. The phthalic acid diester derivative according to claim 1,wherein R² is a tert-butyl group.
 10. The phthalic acid diesterderivative according to claim 1, wherein R³ is a tert-butyl group. 11.The phthalic acid diester derivative according to claim 1, wherein thephthalic acid diester derivative is dineopentyl 4-methylphthalate. 12.The phthalic acid diester derivative according to claim 1, wherein thephthalic acid diester derivative is dineopentyl 4,5-dimethylphthalate.13. The phthalic acid diester derivative according to claim 1, whereinthe phthalic acid diester derivative is dineopentyl 4-bromophthalate.14. The phthalic acid diester derivative according to claim 1, whereinthe phthalic acid diester derivative is dineopentyl 3-fluorophthalate.15. The phthalic acid diester derivative according to claim 1, whereinthe phthalic acid diester derivative is dineopentyl 4-t-butyl phthalate.16. The phthalic acid diester derivative according to claim 1, wherein nis
 1. 17. The phthalic acid diester derivative according to claim 1,wherein n is
 2. 18. The phthalic acid diester derivative according toclaim 1, wherein n=1 and R¹ is a methyl group or a tert-butyl group. 19.The phthalic acid diester derivative according to claim 1, wherein n=2and at least one of the groups R¹ is a methyl group or a tert-butylgroup.